A DFT and TD-DFT Study on Electronic Structures and UV-spectra Properties of Octaethyl-porphyrin with Different Central Metals (Ni, V, Cu, Co)

Publication date: Available online 24 July 2019Source: Chinese Journal of Chemical EngineeringAuthor(s): Xiaoqin Wang, Shiyi Li, Liang Zhao, Chunming Xu, Jinsen GaoAbstractIn this work, the octaethyl-porphyrins with different central metal (M-OEP, M = Ni, VO, Cu, Co) were used to investigate the ground-state molecular structure, electron distribution and UV-spectra properties on molecular level by Density functional theory (DFT). The results showed that the calculation structure parameters of metalloporphyrins agreed well with the experimental value. According to the Natural Bond Orbital (NBO) analysis, the charge distribution of different metalloporphyrins was found that the charge values of the central metal M decreased with the order of VO < Ni < Co < Cu, while the bonding strength between M and the coordinating atom N was VO> Ni> Co> Cu. At the same time, the frontier molecular orbital calculations showed that the SOMO energy of VO (OEP) molecules in the open-shell system was higher than that of Co (OEP) and Cu (OEP), which means that its UV absorption characteristic peak would be red-shifted. In addition, the IEFPCM model of Time-dependent Density functional theory (TD-DFT) was further utilized to simulate the four substance in toluene solution: Co (OEP), Ni (OEP), Cu (OEP) and VO (OEP), and the Soret band peaks were calculated respectively as: 382 nm, 383 nm, 391 nm and 401 nm. Furthermore, the quantitative simulation analysis of metalloporphyrins ...
Source: Chinese Journal of Chemical Engineering - Category: Chemistry Source Type: research